Use of mobile catalysts in the isomerization of hydrocarbons



March 28, 1950 T. B. HUDSON ET AL 2,502,003

USE OF MOBILE CATALYSTS IN THE xsomszaxzmon OF HYDROCARBONS Original Filed Oct. 5, 1942 2 Sheets-Sheet 1 |SOMER|ZAT|ON l6 PRODUCTS y\- PACKED REAcT|oN CHAMBER I 22 A Y T /CAT L 5 2/4 HYDROCARBON FEED CATALYST 3 MAKE-UP 34 46 CATALYST M M PURIFICA n n TION CATALYST FRESH RECYCLE CATALYST SPENT 38 42 MATERIAL INVENTORS THOMAS B. HUDSON BY JOHN D UPHAM ATTORN YS Patented Mar. 28, 1950 USE OF MOBILE CATALYSTS IN THE ISOM- EBIZATION OF HYDROCARBONS Thomas B. Hudson and John D. Upham, Battlesville, kla., assignors to Phillips Petroleum Company, a corporation of Delaware Original application October 5, 1942, Serial No.

60,852. Divided and this application Septembe:- c, 1947, Serial No. 772,556 a 12 Claims.

This invention relates to the catalytic isomerization of hydrocarbons, particularly the lower boiling saturated hydrocarbons such as the paraffins and the cycloparaflins or naphthenes. It has particular application to the formation of branched chain parafllns from less-branched or straight chain parafllns of the same molecular weight, wherein a mobile isomerization catalyst is utilized.

This application is a division of our copending application, Serial No. 460,852, filed October 5, 1942, now Patent No. 2,439,301, issued April 6, 1948.

Isomerization of hydrocarbons has become an important industrial process because of the increased tendency toward high octane number motor fuels, and the development of special uses for certain individual hydrocarbons or groups of hydrocarbons. Thus, the isoparaflins are ordinarily much more valuable than the normal paraflins, both for use per se, and as stock for manufacturing other hydrocarbons by alkylaticn, dehydrogenation followed by polymerization, or other convers on processes. One 01' the most important commercial isomerization processes at the present time is the formation of isobutane from normal butane, using aluminum chloride catalysts. Accordingly, we shall describe our invention with particular reference to such a process, and its application to other isomerizations, and/or other catal sts, will be obvious to those skilled in the art in view of the present disclosure.

The isomerizations with which this invention is concerned are equilibrium reactions; that is, at a given temperature the percentage ofeach of the individual isomers in a mixture of isomers is fixed if equilibrium is attained. For example, if either pure normal butane or pure isobutane be contacted with a suitable catalyst, such as aluminum chloride, under given temperature and pressure conditions permitting the reaction to proceed but preferably avoiding side reactions such as cracking, after a period of time an equilibrium mixture of normal and isobutane will be found. In this mixture, the percentage 01' isobutane will be the same regardless of whether the charging stock was isobutane 0r normal butane. This means that in isomerizing normal butane to produce isobutane,there is a maximum conversion obtainable at any given temperature. The lower temperatures give the greatest conversion, but too low a temperature cannot be used because the reaction rate will decrease to an uneconomic level. On the other hand, higher temperatures give higher reaction rates, but the equitive concentration of normal and isobutane in the 1 mixture at the given time, catalyst activity, and the amount of catalyst surface contacted by the butane, or in other words, on the time of contact of a. unit volume of butane with a unit of catalyst activity.

A large surface area for a given weight of active catalytic material may be obtained by various expedients which are well known in the art. For instance, inert carriers or extenders may be impregnated by or mixed with the catalyst, or the catalyst may be produced in a porous form, or

prepared in a condition of line subdivision as in.

the use 01' small grains or powdered catalyst, which may be suspended in liquid or gaseous hydrocarbons undergoing isomerization. The amount of catalyst surface contacted with reactants is also dependent on the concentration of catalyst in reactants, that is, the amount of catalyst, of whatever kind, mixed with the reactants, or placed in' a stationary bed of catalyst through which the reactants pass, and on the flow rate of reactants through a reaction zone.

Thus it is seen that a number of different reacton conditions influence the rate of reaction, and these reaction conditions frequently vary from point to point in the reaction zone. As the conversion of normal to isobutane occurs in an isomerization zone through which the hydrocarbons are flowing, the decrease in concentration of the normal butane and corresponding increase in concentration of isobutane tends to slow the reaction, particularly as equilibrium is approached. Due to the exothermic nature of this reaction, the temperature has a tendency to increase, causing a tendency toward increased reaction rate. A mobile catalyst becomes deactivated as it passes through the reaction zone, sometimes slightly and sometimes greatly, depending upon the nature of the catalyst and the severity of conditions, and the reaction rate is less at the point of less catalytic activity.

An object of this invention is to provide a process for the'catalytic isomerization of hydrocarbons. Another object is to provide an improved method of contacting catalysts with saturated hydrocarbons to promote molecular rearrangement thereof. A primary object is to correlate the ratio of catalyst activity to reactants throughout an isomerization zone with varying reaction conditions therein so as to maintain substantially constant reaction rates throughout said zone, or at least partially to compensate for said varying reaction conditions. Another obiect is to provide for the rapid attainment of equilibrium conditions and thus decrease the reaction time required for a. given conversion. A further object is to diminish the extent of undesired side reactions such as cracking and the like and thus give increased yields of desired hydrocarbons, improved catalyst life, and other benefits. A further object is to provide improved methods for carrying out isomerization reactions involving a primary catalyst and a promotor, wherein a temperature gradient exists. Yet another object is to provide for the use of mobile isomerization catalysts. A still further object is to provide for the recovery and/or regeneration of such catalysts. Another object is to provide novel methods of conducting isomerization reactions with gaseous, liquid, and/or solid catalysts, wherein said catalysts are introduced multipoint into a reaction zone. Other objects and advantages will become apparent as the disclosure proceeds.

We have now found that the tendencies toward change in reaction rate caused by the varying reaction conditions may be at least partally compensated for, or a substantially constant reaction rate may be maintained, throughout a. reaction zone in which mobile isomerization catalysts are used with flowing streams of liquid and/or gaseous reactants by introducing said catalyst into the reaction zone at a plurality of points, the quantity and/or activity of the catalyst introduced at each point being correlated with the reaction conditions prevailing at that point. Either concurrent or countercurrent flow of catalyst and reactants may be used, depending upon the conditions and the type of catalyst used. The catalyst may be miscible with, or immiscible with the reactants. The various modes of operating in accordance with our invention are not exact equivalents, but may be carried out by one skilled in the 'art by following the basic principles disclosed herein.

The accompanying drawings are provided to better explain the invention, and taken in conjunction With the description thereof, Will serve to exemplify the invention. Figure 1 shows in semi-diagrammatic form suitable apparatus for carrying out the vapor phase isomerization of normal butane, using a fluid melt type of aluminum chloride catalyst, wherein the temperature of the reactant increases durin passage through the reaction zone due to the exothermic nature of the reaction. Figure 2 shows insemidiagrammatic form a series of isomerization zones with associated equipment for effecting isomerization in the liquid phase, with a decreasing temperature gradient to obtain maximum equilibrium yields of isobutane from normal butane.

In Figure 1, the reaction chamber it comprises a'cerami'c-lined vertical tower packed with ceramic-ware raschig rings, stones, or other suit able means for effecting intimate contact between reactants and liquid catalyst. The gaseous iSlIl erization feed which is led into reactor it) through line i2 comprises normal butane, either pure or admixed with minor amountsof isobutane, propane, hydrogen, or other light gases, and anhydrous hydrogen chloride which acts as catalyst activator. This feed must be substantially anhydrous, and may ifnecessary be dehydrated by 4 suitable methods prior to its introduction into chamber Ill. The hydrogen chloride may be in-.

troduced into the reaction chamber in other ways if desired. The feed in line I2 is heated to the proper temperature by means not shown. Suitable temperature and pressure conditions at the inlet of chamber I. are 300 F. and lb. per sq. in. gage. A flow rate of 0.1 to 2.0 liquid volumes of butane per volume of catalyst chamber per hour may be used, and complete equilibrium conversion in one pass is not ordinarily attempted in such a process, the hydrocarbon efliuents comprising from 25 to 50 per cent isobutane, depending upon the flow rate used.

The catalyst composition employed comprises a fluid melt of aluminum chloride with sodium and potassium chlorides, or with halides of other lowmelting metals. The molar ratio of aluminum chloride to the alkali metal chloride should be at least about 1.2 to 1, and greater ratios are advantageous. The catalyst composition is pro muted y a halide of one of the group V metals or a halide of one of the sulfur-group elements of group VI of the periodic system. The fluid catalyst flows through conduit H, and is introduced into reaction chamber 10 at a plurality of points through conduits I6, i8, 20, 22, 24, 26, and 28. It will be understood that more or fewer such conduits may be used, as required by the particular reaction chamber and conversion taking place therein. The catalyst thus introduced into chamber l0 flows downward over the packing material therein, thus presenting an extended surface to the upwardly flowing gases. It will be seen that in this method of operating, the amount of catalyst increases as it flows down the column III, which in turn means that as the reactants flow upward through the column they contact progressively smaller amounts of.catalyst.

As the reactants pass through the reaction chamber, the normal butane is isomerized to isobutane with the evolution of heat. Such heat of reaction is diiilcult to remove from the large reactor, and as a consequence the temperature of the gases rises as they pass upwardly through the reaction chamber Ill. The temperature at the outlet thereof is accordingly appreciably higher than at the inlet, the exact temperature diiference, of course, varying with the particular chamber, type of reaction, flow rate, extent of reaction, etc. In many cases this temperature difference will amount to from 15 to 50 or 60 F. or even more. Such an increase in temperature tends to increase the reaction rate, and in the ordinary methods of isomerization wherein the reactants are passed through a uniform bed of catalyst, the reaction frequently runs-away and is difficult to bring under'control. Increased reaction rate due to increased temperature causes an increased rate of heat evolution, which in turn tends to increase the'temperature' still more. Excessive temperatures caused by such action cause cracking and other undesirable degradation of the butane undergoing reaction, with consequent loss of material, incre ased fractionation load from light gases so-formed. and damage to the catalyst.

' Such an uncontrolled temperature rise is obviated in our process, due to the fact that as the temperature rises, the reactants are contacted with less and less catalyst. The amount of the catalyst at all points in the reaction chamher is correlated with the temperature prevailing at each of said points'," by controlling the amount of catalyst introduced through each of the catalyst conduits along the chamber, and thus the extent of reaction is limited so that in spite of increasing temperature, a substantially constant rate of reaction may readily be maintained throughout the reaction zone if desired. Another advantage is that the limited contact with catalyst of the hottest reactants avoids an undue amount of cracking, so that the isomerization reaction continues at the desiredrate while the ratio of cracking to isomerization is less than it would be at the same temperature if the catalyst concentration were higher.

Other varying reaction conditions operating to influence the rate of reaction are the decreasing concentration of normal butane, and the deactie vatlon of the catalyst occurring as it flows through the reaction zone. As the conversion proceeds, the normal butane concentration drops 6 pm'iflcation system indicated diagrammatically at 40. In this purification, completely spent aluminum chloride and other undesirable mateand that of isobutane increasesso that mass action effects tend to slow the reaction. In the case just discussed, since equilibrium concentrations, at which all reaction will stop, are not closely approached, this factor is not of so much importance, although it must be taken into account in correlating the catalyst activity at points throughout the column with the reaction conditions. The rate of deactivation of the catalyst as it flows through the chamber will depend upon temperature, amount of excess aluminum chloride in the melt, flow rate of reactants, etc. We have found that the countercurrent flow of catalyst and reactants, with multipoint injection of fresh catalyst, has advantage in that the fresh feed is contacted with a relatively large volume of catalyst which is diluted somewhat with spent catalytic material. This is opposite to the ordinary process with concurrent flow of catalyst and reactants, in which the reactants first contact completely fresh catalyst. and our method. even though the total catalyst activity atthe point of flrst contact with reactants may, as in the case described in conjunction with Figure i, be greater than at other points, the dilution eflect of some spent catalyst aids in promoting smooth and regular reaction. In many cases, variation of one of the reaction conditions may have an eifect on reaction rate opposite to that of another varying reaction condition, and in any particular case, the overall effect of the various reaction conditions must be taken into account and correlated with the amount of catalyst introduced at each point.

The isomerization products, which include isobutane, unconverted normal butane, hydrogen chloride, light gases, and traces of C5 and heavier hydrocarbons, leave chamber l0 via line 30, and are passed to conventional treating and separating means not shown. Ordinarily the isobutane is separated as a product of the process, normal butane and hydrogen chloride are recycled, and

light gases may or may not be recycled. Frequently small amounts of hydrogen and/or propane are added to the feed to reduce side reactions, and these gases may be recycled. Certain amounts of propane are formed in the process, and generally separated out from the effluents.

The catalyst melt is removed from the bottom of chamber l0 via conduit 32, and most of it is recycled to conduit I! via line 34 and pump 36. Means other than pumping, such as pressuring with gas, gas-lift, etc. may be used for removing,

the catalyst melt, and the melt may be heated if necessary by means not shown. A portion of the catalyst stream is passed via line 38 to a rials such as heavy hydrocarbons are removed via line 42, and sumcient fresh aluminum chloride is introduced into the catalyst composition via line H to make up for that lost from the process. Catalyst flows from purification 40 to line ll via line 46.

In Figure 2, the isomerization of normal butane is carried out in the liquid phase, using a slurry of finely divided aluminum chloride as the catalyst. The reaction is carried out continuously by concurrent flow of reactants and catalyst through a series of reactors 50, 52, and 54. A greater or smaller number of such reactors may of course be used as conditions warrant. The

hydrocarbon feed, which is predominantly normal butane, is passed in the liquid state from pump 50 at 500 lbs. per sq. in. pressure via line 58 through heat exchanger 60, and continues on via lines 62, 06, and 10 through heat exchangers 64 and 68 to heater 1!, wherein it is brought to the initial reaction temperature, such as 250 F. The thus-heated butane then passes into isomerizer 50 via line H, admixed with suitable amounts of hydrogen chloride activator from line 16 and catalyst from line 18. The catalyst in line 10 can be a slurry and/or solution of aluminum chloride in liquid hydrocarbons, preferably butane, and is pumped by pump or otherwise forced through the system. A heavy oil may sometimes be used to advantage in forming this catalyst composition.

The butane, hydrogen chloride, and aluminum chloride are maintained in constant agitation in isomerizer 50 by means of stirrer 82. Isomerizers 52 and 54 are similarly equipped with stirrers 84 and 86. The continuous flow of material into vessel '50 through line 14 causes a continuous flow of hydrocarbons, hydrogen chloride, and catalyst from vessel 50 to vessel 52 via line 88, this material passing through heat exchanger 68 between the two vessels in order to impart heat to the inflowing butane in line 66, being itself cooled to the temperature around 200 F., required in isomerizer 52. Similarly, material from isomerizer 52 flows to isomerizer 54 via line and heat exchanger 64. A lower temperature, such as It, is maintained in isomerizer 54. It will be understood that vby-passes around the heat exchangers may be provided for controlling the temperatures to the desired extent, and auxiliary heating or cooling means may be provided for the incoming butane feed or the flowing reaction mixture as required.

The isomerizers 50, 52, and 54 are shown to be of the same size as a matter of convenience in the drawing. In actual practice, they may vary in size, depending upon the contact time desired in each of the zones. While any particular molecule of butane may remain in one of the isomerizers for an extremely long or extremely short time, the average time of residence therein is determined by the flow rate or reactants and catalyst and by the volume of the isomerizer.

In the method of operating just described, the total contact time may be chosen readily so that essentially equilbrium conversion is obtained. Since the equilibrium conversion is greatest at low temperatures, it is desirable to complete the reaction at the lowest convenient temperature at which an economic reaction rate may be obtained. However, to carry out the entire isomerization at such a low temperature would require an unneccipient. At such time, the reactants leave chamber 50 and pass on to chamber 52 at a lower temperature, where further conversion is obtained. The flow rate is adjusted so that the residence time at that temperature is sufficient to obtain additional isomerization but insuflicient to allow cracking. The butane finally passes to chamber 54 where it is held at the lowest temperature, for

additional isomerization, generally until substantially equilibrium conversion is obtained. This method of operating at a decreasing temperature gradient is now generally known to the industry,

and is described in Lynch U. S. Patent 2,280,710.

We have found that by introducing the mobile catalyst into the reactants at a plurality of points, the amount introduced at each of said points being correlated with-the particular reaction conditions in the system, a greatly improved operation may be obtained. This is accomplished by introducing the catalyst into the reaction mixture not only into line 14 from line 18, but also into line 08 via line 92 and into line 90 via line 94. In this way, the concentration of catalyst in reactants is increased as the reactants pass through the system at a decreasing temperature gradient. The thus-introducedcatalyst also serves to more than compensate for any catalyst deactivation occurring in the system, and the ratio of catalyst activity to reactants increases in the direction of flow, rather than remaining constant or decreasing as would be the case in the absence of the multipoint introduction of the catalyst.

As stated above, the rate of isomerization decreases with decrease in temperature, and this tendency toward decreased rate is at least par tially compensated for by utilization of our invention, obtaining the advantages of the decreasing temperature gradient, while substantially decreasing the total time required to effect the desired extent of conversion.

Our invention also acts to at least partially overcome the mass action effects of the isobutane present in the reaction zone. As the extent of 0 speeding up the reaction in spite of increasing concentration of isobutane, which is particularly valuable when the equilibrium percentage of isobutane is slowly approached. Thus, the amount of catalyst introduced at each of the points in the system is correlated with temperature and with concentration of reactants to accomplish a more eflicient conversion.

The total isomerization mixture leaves isomerizer 04 via line and heat exchanger 00, and passes to separator 98, wherein catalyst is separated from reactants by gravity settling, centrifuging, filtering, or other means, and is removed, preferably still as a slurry, through line I00. Thus all of the catalyst used in the various parts of the apparatus and introduced at the diflerent points is readily removed from the eflluents in a single separation step. The isomerization eifluents comprising isobutane, normal butane, HCl, and other light gases, as well as small amounts of C5 and heavier hydrocarbons, pass from separator 08 via line I 02 to conventional treatment, separation, etc. not shown. A portion of the catalyst is recycled to the system from line I00 via line 10 and pump 80. Fresh make-up catalyst may be introduced through line I 04. A portion of the catalyst is taken from line I00 through line I00, and may be sent to a purification step wherein recoverable aluminum chloride is separated and returned to the system, while spent material such as inactive aluminum chloride-hydrocarbon complexes and other undesirable matter is removed from the system. r

The invention has been described with particular reference to aluminum chloride catalysts. However, it is to be understood that it is in nowise limited thereto, and may be used in conjunction with many other mobile isomerization catalysts. Other aluminum halides,.particularly aluminum bromide, and various other metal halide isomerization catalysts of the Friedel- Crafts type may be used. Ordinarily halogencontaining promotors, such as hydrogen chloride, hydrogen bromide, etc., or other promotors are used with such catalysts.

While hydrogen fluoride may be used as a promotor for the active metal halide catalysts, it has been found that hydrogen fluoride alone is a very active and versatile isomerization catalyst. Thus the isomerization catalyst used in our invention may comprise essentially hydrogen fluoride, for example, liquid concentrated or substantially anhydrous hydrogen fluoride, or gaseous hydrogen fluoride. The usefulness of this particular catalyst is realized in view of the fact that it may be used in either the liquid or the vapor phase, in contact with liquid or vaporous hydrocarbons. In the liquid phase it may pass concurrently with or countercurrently to liquid and/or gaseous hydrocarbons, and in the vapor phase it may pass concurrently with gaseous or liquid hydrocarbons or countercurrently to liquid hydrocarbons. Thus the particular mode of operating with hydrogen fluoride as an isomerization catalyst is readily chosen to conform with the hydrocarbons undergoing treatment and with the conversion desired. By the multipoint injection of the hydrogen fluoride into the reaction zone, the total catalytic activity is varied from point to point in the reaction zone in inverse ratio to the normal variations of reaction rate from point to point, thus establishing a more desirable reaction rate throughout the zone.

While we have discussed our invention in some detail, and presented various modes of operation, it is not limited to the exact variants shown, but is subject to numerous other modifications. For example, mixtures of fresh or regenerated catalyst along with partially or totally spent catalyst may be introduced into the reaction zone in different proportions at the different points, in order to control the total activity at each point. Reactants, diluents, heat carriers, and the like asoaooa may be used along with the catalyst. These and many other modifications may be utilized in conjunction with the invention, which is to be limited only by the appended claims.

We claim: 7

1. In a catalytic isomerization of saturated hydrocarbons to produce isomeric hydrocarbons of the same molecular weight wherein said hydrocarbons are passed through a reaction zone at isomerizing conditions and wherein a mobile isomerization catalyst substantially immiscible with said hydrocarbons is passed through said reaction zone countercurrent to said hydrocarbons to effect said isomerization, the improvement which comprises introducing said catalyst into said reaction zone at a plurality of points.

2. A process for effecting the isomerization of saturated hydrocarbons utilizing a mobile isomerization catalyst which comprises continuously passing said hydrocarbons through a reaction zone under isomerizing conditions of temperature and pressure such that an increasing temperature gradient exists in the direction of flow of hydrocarbons, and introducing said catalyst into said reaction zone at a plurality of points spaced along the line of flow of said hydrocarbons for flow countercurrent to said hydrocarbons, the activity of the catalyst introduced at said points being such that the ratio of total catalyst activity to hydrocarbons in said reaction zone decreases in the direction of flow of hydrocarbons.

3. The process of claim 1 in which said saturated hydrocarbons comprise normal butane. in which the isomerization is effected with the hydrocarbons in the vapor phase and in which the catalyst comprises aluminum chloride.

, 4. The'process of claim 1 in which said catalyst comprises a halide catalyst of the Friedel- Crafts type.

- 5. The process of claim 1 in which said catalyst comprises an aluminum halide.

6. The process of claim 1 in which said catalyst comprises aluminum chloride.

'7. The process of claim 1 in which said catalyst comprises hydrogen fluoride.

8. The process of claim 1 in which low-boiling paraflin hydrocarbons are isomerized to more branched paraflln hydrocarbons.

9. The process of claim 1 in which naphthene hydrocarbons are isomerized.

10. A process for the vapor-phase exothermic isomerization of normal butane to isobutane which comprises passing a gaseous stream other-- 10 mal butane upwardly through a vertical reaction zone under isomerization conditions sulficiently adiabatic to cause an increase in temperature in the direction of flow of said stream tending tocause an increase in reaction rate, introducing into said reaction zone at a plurality of points'spaced along the line of flow a liquid aluminum chloride-containing isomerization catalyst and flowing same downwardly through said zone in intimate contact with said rising stream of butane. vapors, and separately controlling the quantity and activity of catalyst introduced at each of said points to decrease the ratio of catalyst activity to hydrocarbons in the direction of flow of said hydrocarbons as an inverse function of temperature so that less catalyst is progressively contacted by said butane stream as it fiows upwardly through said reaction zone at increasing temperature, whereby the aforesaid tendency toward increase in reaction rate is counteracted and a substantially constant reaction rate is established throughout said reaction zone.

11. The process of claim 10 in which said liquid catalyst comprises a fluid melt of aluminum chloride with at least one alkali metal chloride.

12. In a process for effecting the isomerization of a saturated hydrocarbon in a reaction zone wherein a countercurrent flow of the hydrocar bon and a mobile catalyst .is maintained under isomerizing conditions and wherein in the direction of flow of the hydrocarbon through said zone there exists an increasing temperature gradient, the step of introducing said catalyst in.

masses at a plurality of points respectively along the line of flow of said hydrocarbons thus causing a decrease in the ratio of total catalyst activity to said hydrocarbons in the direction of flow of said hydrocarbons.

' THOMAS B. HUDSON.

JOHN D. UPHAM.

REFERENCES orrsn The following references are of record in the Hudson et al. a Sept. 2. 1947 

1. IN A CATALYTIC ISOMERIZATION OF SATURATED HYDROCARBONS TO PRODUCE ISOMERIC HYDROCARBONS OF THE SAME MOLECULAR WEIGHT WHEREIN SAID HYDROCARBONS ARE PASSED THROUGH A REACTION ZONE AT ISMERIZING CONDITIONS AND WHEREIN A MOBILE ISOMERIZATION CATALYST SUBSTANTIALLY IMMISCIBLE WITH SAID HYDROCARBONS IS PASSED THROUGH SAID 